Complex organo silicon compounds

ABSTRACT

This invention is addressed to complex organo silicon compounds prepared by reaction of a halosilane, an alkylene oxide and a complex epoxide containing at least one other functional group. The products of this invention are liquid organosilicon compounds which are useful in the treatment of glass fibers to improve the bonding relationship between glass fibers and resinous or elastomeric materials.

United States Patent [1 1 Foley et. al.

[ Aug. 12, 1975 COMPLEX ORGANO SILICON COMPOUNDS [75] Inventors: Kevin M. Foley, Hebron; Francesco M. Vigo, Heath both of Ohio [73] Assignee: Owens-Corning Fiberglas Corporation, Toledo, Ohio [22] Filed: Apr. 2, 1973 [21] Appl. No.: 347,264

[52] U.S. Cl. ..260/448.8 R; 117/126 GS: 117/126 GN; 260/348 SC [51] Int. Cl. C07f 7/18 [58] Field of Search 260/448.8 R

[56] References Cited UNITED STATES PATENTS 2,496,335 2/1950 Christ 260/4488 R 2,730,532 1/1956 Martin 260/448.8 R X 2,883,395 4/1959 Rogers et al. 260/4488 R X 3,369,006 2/1968 Brown 260/448.8 R X Primary Examine'r-Paul F. Shaver Attorney, Agent, or Firm-Car1 G. Staelin; John W. Overman; Keith V. Rockey 7 ABSTRACT 49 Claims, No Drawings 1:1 COMPLEX ORGANO SILICON COMPOUNDS rubber tires and the like, it has been the practice to treat the glass fibers with organo silicon compounds.

The organo silicon compounds frequently used for this purpose are the organo silanes of the formula RSi(OR') (1) wherein R is an organic group which may contain any of a variety of functional groups, such as amino, epoxy, hydroxy, mercapto, etc., and R is an alkyl group. While such silanes as well as their hydrolysis products and polymerization products are quite effective in promoting a secure bonding relationship between glass fibers and resins and elastomeric materials, they are nevertheless expensive to manufacture and consequently contribute to the overall costs in the manufacture of glass fiber reinforced resins and elastomeric materials.

It is known, as shown by US. Pat. No. 2,650,934, that an alkylene oxide can be reacted with silicon tetrahalides such as silicon tetrachloride as follows:

.this reaction, which is disclosed in US. Pat. No.

3,169,884, the product does not contain the stabilized It is an object of the present invention to produce complex organo silicon compounds which contain betahaloalkoxy groups attached directly to the silicon atoms which stabilize the compounds against hydroly sis.

It is a more specific object of this invention to produce organo silicon compounds which contain highly reactive functional groups along with beta-haloalkoxy groups for use in the treatment of highly hydrophilic substrates to render such substrates more hydrophobic.

The concepts of this invention reside in complex organo silicon compounds which are prepared by reaction of a halosilane with at least one alkylene oxide and at least one other organo epoxide containing at least one other functional group. As will be appreciated by those skilled in the art, the nature of the product depends not only upon the specific combination of epoxides employed but also upon the reactant proportions.

In all cases, however, the reaction product includes a mixture of compounds which can be utilized as such or,

if desired: the predominant compounds forming the reaction product can be separated in relatively pure form.

As the other epoxide, use is preferably made of organic epoxides containing at least one other functional group. By way of illustration, the following compounds can be employed:

[ l] Epoxides of the formula wherein R is an aryl group such as phenyl or phenyl substituted with an amino group, a halogen group, an alkyl group; alkyl containing 1 to 20 carbon atoms and substituted derivatives thereof; an alkenyl group con taining 2 to 8 carbon atoms (e.g., vinyl, allyl, etc.); styrene oxide; a group having the formula wherein R is hydrogen or methyl, Illustrative of such epoxides are phenyl glycidyl ether, cresyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, a mixture of n-octyl and n-decyl glycidyl ethers (Epoxide No. 7 from Procter and Gamble) and a mixture of n-dodecyl and n-tetradecyl glycidyl ethers (Epoxide No. 8 from Procter and Gamble).

[2] Epoxides of the formula (DER 73h) (Ill (Di-LR 732) [3] Cycloalkane epoxides, including the following:

-CH-C o 2 (RD 4 or ERL 4206) (l6) (ERR 4205) 0 0 CH 0 c (CH (i 0 CH CH CH -c 0 CH2 0 ll 0 In accordance with one embodiment of the invention, the organo silicon compounds are prepared by reaction of from 1 to 3 epoxide equivalents of the alkylwherein X represents halogen, R is hydrogen or C to C alkyl (e.g., methyl, ethyl, propyl, etc.), and R is hydrogen or C to C alkyl, and preferably hydrogen, a represents the epoxide equivalent of the alkylene oxide and b represents the epoxide equivalent of the epoxide containing a functional group In actual practice, the reaction products produced is a mixture of compounds which can be utilized as such without the need to separate specific compounds contained in the reaction product.

However, compounds contained in'the reaction mixture can be, if desired, separated from the mixture by known techniques, such as fractional distillation, liquid chromatography, etc., to yield the substantially pure compounds. Such compounds frequently depend upon the epoxide equivalents employed, that is, the values of a and b. For example, when the reaction mixture contains about 2 to 3 epoxide equivalents of the alkylene oxide and about 1 to 2 epoxide equivalents of the epoxide containing the functional group, the reaction product includes the following compounds:

wherein x is an integer from 2 to 3 and y is an integer from 1 to 2, and

X X X ene oxide and at least 0.5 and up to 3 epoxide equivawherein x is 3 and y is l and where X, R R and R are lents of the epoxide containing a functional group per mole of the silicon tetrahalide. As used herein, the term epoxide equivalent refers to the number of moles of the epoxide divided by the number of epoxide groups as described above, as well as the corresponding derivatives where the epoxide is a cyclohexane epoxide.

Examples of specific compounds which can be prepared in accordance with the present invention include per molecule. Thus, this reaction may be illustrated by the following:

the following:

(SiCl 1 mole; propylene oxide 3 equivalents; DER 332 l 0 CH3 Cl Cl (29) 5 ll x (CH CH CH2 OMSFO CHZ CH CH2 O C CH=CH2 (SiCl 1 mole; propylene oxide 3 equivalents; glycidyl l l methacrylate 1 equivalent) Cl Cl (3m c H 3 k 1 p py Oxide 3 q l n g y y (SiCl 1 mole; ethylene oxide 3 equivalents; cresyl glycerylate 1 equivalent) l5 idyl ether 1 equivalent) (CH;;-CHCH2O ):iSi--OCH CH l Cl Cl 20 :I R 2 )il 2 2 ID 2I Cl Cl (31 (SiCl 1 mole; propylene oxide 3 equivalents; styrene oxide 1 equivalent) (SiCl 1 mole; propylene oxide 3 equivalents; decyl (CH;t 2 )n 2? 25 glycidyl ether l equivalent) k 1 mole; P py Oxide 3 equivalentsfERE (SiCl 1 mole; propylene oxide 3 equivalents; tetra- 359 1 qui decyl glycidyl ether 1 equivalent) (SiCl 1 mole, propylene oxide 3 equivalents; DER 736 (SiCl 1 mole; propylene oxide 3 equivalents; phenyl- (SiCl, 1 mole; propylene oxide 3 epoxide equivalents; reactiontemperature is not critical in: reaction gen- RD 4 l epoxide equivalent) I erally takes place spontaneously and evolves heat. Best ((Y'H,,(!'H-('H --(h,,si -O O Sim -('l'l. ."-(ll (H,.,l,,

l (l (l C1 C1 (as,

(SiCl, 1 mole; propylene oxide 3 epoxide equivalents; results are usually achieved when the reaction tempera- ERR 4205 1 epoxide equivalent) O ture is maintained below 100C, such as within the o 0 II H ((H: -(H Si 0 (H. --O-(-( (H 1 --C-- -(H o '--$i(0--(H --("H.

I Br Br C H Br c H 3 3 (3m (SiBr 1 mole; ethylene oxide 3 epoxide equivalents; range of 0 to 100C. ERR 4289 l epoxide equivalent) Where the epoxide containing the functional group Cl Cl (SiCl 1 mole; butyl e o id 3 id i l t as described above contains two or more epoxide ERR 4221 l e oxide equi l nt) groups, it is frequently preferred that the alkylene 0 CH3 oxide be added to the halosilane prior to the time that H CH CHO O CH CH CH 0 g i the diepoxide is added to the reaction mixture. This (C I 2 )2 K procedure has the advantage that the reaction of alkyl-- Cl Cl (38) ene oxide with the silicon tetrahalide is quite exothermic and thus raises the temperature of the reaction me- (SiCl 1 mole; propylene oxide 2 epoxide equivalents; dium to a level suitable for addition of the epoxide conglycidylmethacrylate 2 epoxide equivalents) taining the functional grouping.

Where the epoxide containing the functional group ide can be added to the reaction, mixture before the (I (l (39) other, or they may be added simultaneously.

Where the reaction mixture contains 2 or more equivalents of an epoxide containing 2 or more epoxide groups per molecule, the reaction product includes 1 compounds in which one of the epoxide groups in the (CH ClCH O),Si(OCH -CH-CH 0 40 functional epoxide remains unreacted with the silicon tetrahalide. For example, when the functional epoxide is one of those defined by (6) above, the reaction product includes compounds (SiCl 1 mole; propylene oxide 2 epoxide equivalents; 40 allylglycidyl ether 2 epoxide equivalents) (SiCl 1 mole; ethylene oxide 2 epoxide equivalents; glycidylphenyl ether 2 epoxide equivalents) Where the epoxide containing the functional group (R CH CH -Q) Si O CH ({H R CH includes two or more epoxide groups, it is generally X X 0 preferred that the equivalents of the alkylene oxide a be at least 2.2 and preferably at least 2.5 to avoid poly- (41) mer formation which leads to gelling of the reaction product.

In preparing the reaction mixtures of the present inwhere R R R and X are as described above. vention, the reactants are contacted in the liquid phase. Such compounds include the following:

((H ,(|H-(H ());,Si )-(H:qH--('H ()(H2CH (H. J

An inert organic solvent can be employed, if desired, (SiCl 1 mole; propyl n Oxide 3 equivalents; ERE but is not essential to the practice of the invention. The 1359 2 equivalents) (SiBr, l mole; ethylene oxide 2 equivalents; ERE 1359 2 equivalents) (I 0 cu,

(SiCl 1 mole; propylene oxide 2 equivalents; DER 332 2 equivalents) It will be observed that in all of the compounds specifically described above, with the exception of the product prepared from styrene oxide, each bond to the silicon atom contains a beta-haloalkoxy group. As indicated above, it is believed that such groupings impart improved stability to the compounds of the invention.

In accordance with another concept of the present invention, all or a part of the alkylene oxide reactant can be substituted by an alcohol, and preferably a monohydric alcohol. For this purpose, use can be made of an alkanol ROI-l where R is alkyl containing 1 to 6 carbon atoms. However, a variety of other alcohols may likewise be employed including benzyl alcohol, allyl alcohol, alkanol amines containing 2 to 6 carbon atoms such as ethanol amine, propanolamine, butanolamine, etc, as well as numerous other alcohols.

group is a monoepoxide, all of the reactants can be added simultaneously or in any desired order.

The reaction product is generally a mixture of compounds depending on the nature of the reactants and proportions. It is generally preferred that the reaction mixture contain 1 to 3 moles of the alcohol, 0 to 2 epoxide equivalents or more of the alkylene oxide and 0.5 to 3.0 epoxide equivalents of the epoxide containing a functional group per mole of SiX Where the latter is a diepoxide, it is preferred that the total of the moles of alcohol and alkylene oxide be at least 2.1 and preferably at least 2.5 to minimize polymer formation and gelling of the reaction product.

Specific compounds of this type include:

(SiCl 1 mole; CH OH 3 hydroxy equivalents; glycidylacrylate 1 epoxide equivalent) where R is alkyl containing 1 to 6 carbon atoms derived from the alkanol, benzyl, allyl or aminoalkyl containing 2 to 6 carbon atoms, derived from the alkanolamine, R R R and X are as described above; and c is the number of hydroxy equivalents used, which ranges from 1 to 3, and d is the number of epoxide equivalents of the alkylene oxide, which ranges from O 60 (SiCl 1 mole; Cl- 0H 2 hydroxy equivalents; propylene oxide 1 epoxide equivalent; glycidylacrylate 1 epoxide equivalent) (SiCl 1 mole; benzyl alcohol 3 hydroxy equivalents; allylglycidyl ether 1 epoxide equivalent) (SiCl 1 mole; allyl alcohol 3 hydroxy equivalents; allylglycidyl ether 1 epoxy equivalent) (SiCl 1 mole; CH OH 3 hydroxy equivalents; RD 2 2 epoxide equivalents) (SiCL, 1 mole; allyl alcohol 3 hydroxy equivalents; ERE 1359 2 epoxide equivalents) (SiCL, 1 mole; C H Ol-l 2 hydroxy equivalents; 'propylene oxide 1 epoxide equivalent; DER 332 2 epoxide equivalents) Specific compounds of this type include:

lene oxide l epoxide equivalent; RD 2 l epoxide equivalent) (SiCl 1 mole; benzyl alcohol 3 hydroxy equivalents;

5 ERE l359 l epoxide equivalent) (SiCL, 1 mole; allyl alcohol 3 hydroxy equivalents; DER

35 736 l epoxide equivalent) (SiCl; l mole; CH OH 3 hydroxy equivalents; ERR 4289 2 epoxide equivalents) (SiCl' 1 mole; CH Cl-I OH 3 hydroxy equivalents; RD 4 2 epoxide equivalents) Cl C (M;

(SiCL, 1 mole; ethanolamine 3 hydroxy equivalents; ERR 4205 2 epoxide equivalents) In. accordance with yet another embodiment of the invention, the halosilane employed in the reaction can contain one or more organo groups attached directly to the silicon atom through a carbon-to-silicon bond. In the preferred practice of this embodiment of the invention, the halosilane is of the formula wherein R is an organic group containing 1 to carbon atoms, n is an integer from 1 to 2 and X is halogen and preferably chlorine or bromine.

R is preferably alkyl containing 1 to 20, and preferably 1 to 6 carbon atoms (e.g,, methyl, ethyl, propyl, isopropyl, lauryl, etc.); alkenyl containing 2 to 20 and preferably 2 to 6 carbon atoms (e.g. vinyl, allyl, 3- butenyl, 4-pentenyl, etc), cycloalkyl, such as cyclopentyl, cyclohexyl, etc., phenyl, as well as substituted derivatives thereof.

Where the organo halosilanes described above are reacted with an alkylene oxide and an epoxide containing a functional group as described above, it is preferred to employ from 1 to 2.5 epoxide equivalents or moles of the alkylene oxide per mole of the halosilane and from 0.5 to 3 epoxide equivalents of the epoxide containing the functional group per mole of the halosilane. Where the latter epoxide contains two epoxide groups and n 1, it is desirable to employ at least 1.2 and preferably at least 1.5 epoxide equivalents of the alkylene oxide to minimize gel formation.

As is the case in the embodiments described above, the reaction product is usually in the form of a mixture of compounds. However, compounds which can be separated from the reaction products include:

where R R R and X are as described above and e is an integer from 1 to 2, and f is an integer from 1 to 2, with the total of e and f being equal to 3 where n is 1, and to 2 where n is 2;

and/or Specific compounds which can be prepared in accordance with the concepts of the invention include:

Cl X

(Cl-l SiCl 1 mole; propylene oxide 2 epoxide equivalents; glycidyl phenyl ether 1 epoxide equivalent) (CH =CHSiCl;, 1 mole; propylene oxide 2 epoxide equivalents; allylglycidyl ether 1 epoxide equivalent) (CH =CHSiCl 1 mole; propylene oxide 1 epoxide equivalent; glycidyl acrylate l epoxide equivalent) (allyltrichlorosilane 1 mole; propylene oxide 2 epoxide equivalents; glycidylmethacrylate 1 epoxide equivalent) (ethyltrichlorosilane 1 mole; propylene oxide 2 epoxide equivalents; ERE 1359 2 epoxide equivalents) (CH =C1-1SiCl 1 mole; ethylene oxide 1 epoxide equivalent', RD 2 2 epoxide equivalents).

As will be appreciated by those skilled in the art, the alkylene oxide can be replaced in whole or in part by a monohydric alcohol of the type described above, In general, it is preferred to employ from 1 to 2 moles of the alcohol and O to 2 moles of the alkylene oxide per mole of the organo silane. The order of reaction is not critical, but it is frequently preferred to react the alcohol and/or alkylene oxide with the silane prior to reaction with the epoxide when the latter contains 2 or more epoxide groups per mole.

The reaction product is generally-a mixture of compounds; however, compounds which are included in the mixture and which can be separated therefrom include compounds such as R;-Si(OR OCH CHR, ),,(OCH4 ,CHCHv ,OR

wherein R R R R and X are as described above, g is an integer from 1 to 2 and h is an integer from O to l.

Specific compounds which can be prepared in accordance with this embodiment include:

Cl (CH =CHSiCl 1 mole; CH OH 2 moles; allylglycidyl ether 1 mole) (CH =CHSiCl 1 mole; CH OH 3 mole; propylene oxide 1 mole; DER 332 l epoxide equivalent) (CH =CHSiCl;, 1 mole; CH CH OH 2 moles; RD 2 2 epoxide equivalents).

If desired, in the practice of this embodiment of the invention, the reaction can be carried out using a monoepoxide containing a functional group alone. This reaction frequently produces specific compounds but can also result in mixtures. Compounds produced include the following types:

R Si(OCH (fHCH OR (85) X Representative of specific compounds include the following:

CH =CH-Si( OCl-l CHCH -OCH CH=CH- (86) (CH SiCL, 1 mole; CH3OH 1 mole; propylene oxide 1 mole; phenyl glycidyl ether 1 mole) (CH =CHSiCl 1 mole; CH OH 2 moles; glycidylacrylate 1 mole) (CH =CHSiCl 1 mole; glycidylacrylate 3 epoxide equivalents) (CH =CHSiCl 1 mole; allyl alcohol 1 mole; ethylene oxide 1 mole; methyl glycidyl ether 1 mole) Where the epoxide contains two epoxy groups per 40 mole, the compounds include:

and/or 45 (allyltrichlorosilane 1 mole; glycidylmethacrylate 3 ep- (CH SiCl 1 mole; CH OH 2 moles; ERE 1359 l epoxide equivalent) I l s I oxide equivalents) 17 (CH;,SiCl;, 1 mole, cresyl glycidyl ether 3 epoxide equivalents) CH CHSKo era-CH"Gi o-c, (90

duced in accordance with the concepts of this invention can be used in a wide variety of applications in which the organo silicon compounds described in formula (l above have been used. It has been-found that the organo silicon compounds of this invention are ef fective in the treatment of glass fibers to improve the bonding relationship between glass fibers and resinous plastics and elastomeric materials. For example, the compounds of this invention or the mixtures of compounds produced in accordance with this invention can be applied as a thin coating to individual glass fiber filaments and the coated glass fiber filaments can then be employed as reinforcement for resins and elastomeric materials. Alternatively, the compounds and mixtures of compounds prepared in accordance with this invention can be formulated into impregnating compositions for use in the impregnation of bundles of glass fibers for reinforcement of elastomeric materials as in the manufacture of glass fiber reinforced elastomeric products including rubber tires, drive belts, timing belts, etc.

Having described the basic concepts of the present invention, reference is now made to the following examples which are provided by way of illustration, and notby way of limitation, of the practice of this invention.

EXAMPLE l 4 Into a round bottom flask equipped with a stir rod, a thermometer and a reflux condenser, there is introduced 1 mole of silicon tetrachloride. Thereafter, 3 moles of propylene oxide are slowly added to the reaction which is accompanied by the evolution of heat. After addition of the propylene oxide, 0.5 mole (1 epoxide equivalent) of the diepoxide DER 332 (compound No 13) is added to the flask. The resulting mixture is then allowed to stand for 1 hour.

Analysis of the reaction product reveals the presence of a mixture of compounds. From this mixture there is separated the organo silicon compound identified as (23) above.

EXAMPLE 2 EXAMPLE 3 Using the procedure described in Example 1, l mole of silicon tetrachloride isreacted with 3 moles of propylene'oxide and 1 mole of styrene oxide. The reaction product, which is a mixture of compounds, is foundto contain the compound (25). i

18 EXAMPLE 4 Using the procedure described in Example I, 1 mole of silicon tetrachloride is reacted with 3 moles of propyleneoxide and l mole l epoxide equivalent) of allyl glycidyl ether. The reaction mixture is found to contain compound (26) which can be separated therefrom in a conventional manner.

EXAMPLE 5 Using the procedure described in Example 1, 1 mole of silicon tetrachloride is reacted with 3 moles of propylene oxide and 0.5 mole l epoxide equivalent) of epoxide ERE 1359. The reaction product is analyzed and is found to contain a mixture of compounds. Compound (27) can be separated therefrom in a conventional manner.

EXAMPLE 6 Using the procedure described in Example 1, 1 mole of silicon tetrachloride is reacted with 3 moles of propylene oxide and 0.5 mole (1 epoxide equivalent) of epoxide DER 736. The reaction product can be used in the treatment of glass fibers without further purification, if desired.

EXAMPLE 7 Using the procedure described in Example 1, 1 mole of silicon tetrachloride is reacted with 3 moles of propylene oxide and 1 mole 1 epoxide equivalent) of glycidyl methacrylate. The reaction product is found to include compound (29) which can be separated therefrom by liquid chromatography.

EXAMPLE 8 Using the procedure described in Example 1, 1 mole of silicon tetrachloride isreacted with 3 moles of ethylene oxide and 1 mole (l epoxide equivalent) of cresyl glycidyl ether. The product is found to include compound (30) which can be separated from the mixture in a conventional manner.

EXAMPLE 9 Using the procedure described in Example 1, 1 mole of silicon tetrachloride is reacted with 3 moles of propylene oxide and 0.5 mole l epoxide equivalent) of Epoxide RD 4. The product is found to include compound (34) which can be separated therefrom by liquid chromatography.

EXAMPLE 10 Using the procedure described in Example l, 1 mole of silicon tetrachloride is reacted with 3 moles of propylene oxide and 0.5 mole (1 epoxide equivalent) of Epoxide ERR 4205. The product is found to include compound (35) which can be separated therefrom if desired.

EXAMPLE 1 l Using the procedure described in Example 1, 1 mole of silicon tetrachloride is reacted with 3 moles of 1,2- butylene oxide and 0.5 mole (l epoxide equivalent) of epoxide ERR 4221. The reaction product, which is a mixture of compounds, is found to contain compound (37) which can be separated therefrom in a conventional manner.

EXAMPLE 12 Using the procedure described in Example l, 1 mole of silicon tetrachloride is reacted with 2 moles of propylene oxide and 2 moles (2 epoxide equivalents) of glycidyl methacrylate. The reaction product is found to contain compound (38) which can be separated, if desired.

EXAMPLE l 3 Using the procedure described in Example 1, l mole of silicon tetrachloride is reacted with 2 moles of propylene oxide and 2 moles of Procter and Gamble Epoxide N0. 7. The reaction product can be used in the treatment of glass fibers without further purification, if desired.

EXAMPLE 14 1 mole of silicon tetrachloride is reacted with 2 moles of propylene oxide and 2 moles (l epoxide equivalent) of allyl glycidyl ether. The reaction product is found to contain compound (39) which can be separated if desired.

EXAMPLE l 1 mole of silicon tetrachloride is reacted with 2 moles of ethylene oxide and 2 moles (2 epoxide equivalents) of phenylglycidyl ether. The reaction product is found to contain compound (40) which can be separated therefrom if desired.

EXAMPLE 16 Using the procedure described in Example 1, 1 mole of silicon tetrachloride is reacted with 2 moles of propylene oxide and 1 mole (2 epoxide equivalents) of epoxide ERE 1359. The viscous reaction product is found to include compound (42) which is separated from the mixture by liquid chromatography.

EXAMPLE l7 1 mole of silicon tetrachloride is reacted with 2 moles of propylene oxide and 1 mole (2 epoxide equivalents) of epoxide RD 4. The product is found to contain compound (44) which can be separated therefrom by conventional techniques.

EXAMPLE 18 Using this procedure described in Example 1, 1 mole of silicon tetrachloride is reacted with 2 moles of propylene oxide and 1 mole (2 epoxide equivalents) of epoxide DER 332. The reaction mixture is found to contain the compound (45) which can be separated from the mixture.

EXAMPLE l9 1 mole of silicon tetrachloride is reacted with 3 moles (3 hydroxy equivalents) of methanol and the product of this reaction is then reacted with 1 mole (l epoxide equivalent) of glycidyl acrylate. The product of this reaction is found to be a mixture of compounds. Compound (46) can be separated from the mixture by liquid chromatography.

EXAMPLE 2O 1 mole of silicon tetrachloride is reacted with 2 mole (2 hydroxy equivalents) of methanol and the product of this reaction is reacted with 1 mole l epoxide equivalent) of propylene oxide. The resulting product is reacted with 1 mole l epoxide equivalent) ofyglycidyl acrylate. This reaction product is found to be a mixture of compounds, one of which is identified as compound (50) which can be separated from the mixture by conventional techniques.

EXAMPLE 2] Using the procedure described in Example l9, 1 mole of silicon tetrachloride is reacted with 3 moles of allyl alcohol and the resulting product is then reacted with 1 mole of allylglycidyl ether. The crude reaction mixture, which is formed of a mixture of compounds, is found to include compound (52) which can be separated from the mixture.

EXAMPLE 2 Using the procedure described in Example 19, 1 mole of silicon tetrachloride is reacted with 3 moles of methanol and 1 mole (2 epoxide equivalents) of epoxide RD 2. The resulting product is found to contain compound (54) which can be separated from the reaction mixture, if desired.

EXAMPLE 23 Using the procedure described in Example l9, 1 mole of silicon tetrachloride is reacted with 3 moles (3 hydroxy equivalents) of ethanol amine. The resulting product is then reacted with 1 mole l epoxide equivalent) of cresyl glycidyl ether. The reaction product, which is a mixture of compounds, is found to contain compound (53).

EXAMPLE 24 1 mole of silicon tetrachloride is reacted with 1 mole of methanol and 1 mole of propylene oxide. Thereafter, the resulting product is reacted with 1 mole (2 epoxide equivalents) of epoxide ERR 4289.

EXAMPLE 25 1 mole of silicon tetrachloride is reacted with 3 hydroxy equivalents (3 moles) of benzyl alcohol and the resulting product is then reacted with 1 mole (2 epoxide equivalents) of epoxide ERE 1359. The product is found to contain significant amounts of compound (60).

EXAMPLE 26 Using the procedure described in Example 26, 1 mole of vinyltrichlorosilane is reacted with 2 epoxide equivalents (2 moles) of propylene oxide. The reaction product is then reacted with 1 mole of allylglycidyl ether. The resulting product is found to contain compound in significant amounts.

EXAMPLE 2% Using the procedure described in Example 26, 1 mole of allyltrichlorosilane is reacted with 2 moles (2 epoxide equivalents) of propylene oxide and the product of this reaction is reacted with 1 mole (l epoxide equivalent) of glyeidylmethacrylate. The product is found to contain compound (72) which can be sepa rated from the reaction mixture by conventional techniques.

EXAMPLE 29 1 mole of vinyltrichlorosilane is first reacted with 2 moles of ethylene oxide and the resulting product is then reacted with epoxide RD 2 (2 epoxide equivalents). The reaction product is found to contain compound (74) in admixture with other organo silicon compounds.

EXAMPLE 30 1 mole of vinyltrichlorosilane is reacted with 2 moles of methanol and the resulting product is then reacted with l mole of allylglycidyl ether. The reaction product is found to contain compound (76) in relatively high yields.

EXAMPLE 31 Using the procedure described in Example 30, 1 mole of methyltrichlorosilane is reacted with 1 mole of methanol and 1 mole of propylene oxide. The resulting product is then reacted with 1 mole of glycidylphenyl ether and the reaction product is found to contain compound (77) which ean be separated by conventional techniques.

EXAMPLE 32 Using the procedure described in Example 30, 1 mole of vinyltrichlorosilane is reacted with 1 mole of methanol and l mole of propylene oxide. Thereafter, the reaction product is contacted with epoxide DER 332 l epoxide equivalent) to produce a mixture which is found to contain compound (83).

EXAMPLE 33 1 mole of vinyltrichlorosilane is reacted with 3 moles of allylglycidyl ether. The reaction product is found to contain predominantly compound (86).

EXAMPLE 34 We claim:

1. Organo silicon compounds prepared by reaction of (l a halosilane selected from the group consisting of a silane of the formula SiX wherein X is halogen, and a compound of the formula (R ),,SiX wherein R is an organic group selected from the group consisting of alkyl, alkenyl, cycloalkyl and phenyl. X is halogen and n is an integer from 1 to 2, with (2) a compound selected from the group consisting of a monohydric alcohol, an alkylene oxide and a combination thereof and (3) an epoxide selected from the group consisting of an epoxide of the formula C Hg-CH-C H2-O-R2 wherein R is selected from the group consisting of phe nyl and the amino, halogen and alkyl substituted derivatives thereof, alkyl, alkenyl, acrylo and methacrylo; styrene oxide; an epoxide of the formula CH -CHCH R CH CH-CH O 0 wherein R is a divalent organic group selected from the group consisting of alkylene, alkyleneoxyalkylene,

oxyalkyleneoxy, oxyalkyleneoxyalkyleneoxy, a group having the formula and a group having the formula and a cyclohexane epoxide, with the ratio of the number of epoxide equivalents of (3) to the number of moles of (l being less than 2 when the epoxide (3) contains two or more epoxy groups per mole.

2. Compounds as defined in claim 1 wherein the halosilane is SiX and the reaction is carried out with l to 3 epoxide or hydroxy equivalents of said compound and l to 3 epoxide equivalents of (3) per mole of the halosilane.

3. Compounds as defined in claim 1 wherein X is selected from the group consisting of chlorine and bromine.

4. Compounds as defined in claim 1 wherein the halosilane is SiX 5. Compounds as defined in claim 4 wherein said compound is an alkylene oxide.

6. Compounds as defined in claim 4 wherein said compound is a monohydric alcohol.

7. Compounds as defined in claim 4 wherein said compound is a mixture of an alkylene oxide and a monohydric alcohol.

8. Compounds as defined in claim 1 wherein the halosilane is (R ),,SiX

9. Compounds as defined in claim 1 wherein the halosilane is R SiX l0. Compounds as defined in claim 9 wherein the reaction is carried out with l to 2 epoxide or hydroxy equivalents of said compound and l to 2 epoxide equivalents of (3) per mole of the halosilane.

l l. Organo silicon compounds prepared by reaction of a halosilane of the formula SiX wherein X is halogen with an alkylene oxide and an epoxide having the formula wherein R is selected from the group consisting of phenyl and the amino, halogen and alkyl substituted derivatives thereof, alkyl, alkenyl. acryl and methacryl.

12. Compounds as defined in claim 11 wherein the reaction is carried out with 1 to 3 epoxide equivalents of the alkylene oxide and l to 3 epoxide equivalents of said epoxide.

13. Compounds as defined in claim-11 wherein the product includes compounds of the formula and wherein R is hydrogen or alkyl.

14. Organo silicon compounds prepared by reaction of a halosilane of the formula SiX with an alkylene oxide and an epoxide having the formula CH CHCH R CH CHCH wherein R is a divalent organic group selected from the group consisting of alkylene, alkyleneoxyalkylene, oxyalkyleneoxy, oxyalkyleneoxyalkyleneoxy, a group of the formula and a group of the formula where R is hydrogen or alkyl.

16. Compounds as defined in claim 14 wherein the product includes compounds of the formula wherein R is hydrogen or alkyl.

17. Compounds as defined in -i wherein the reaction is carried out by rota mg the alkylene oxide with the halosilane and then reacting the resulting product with said epoxide.

18. Organo silicon compounds prepared by reaction of a halosilane of the formula SiX 'wherein X is halogen with an akylene oxide and a cyclohexane epoxide selected from the group consisting of CH-CH2 o o o o o cH -o-i: (CH2) 4-JJO-CH2 0 CH 3 CH3 with the ratio of the number of epoxide equivalents of the cyclohexane epoxide to the number of moles of the halosilane being less than 2.

19. Compounds as defined in claim 18 wherein the reaction is carried out with 2.l to 3.0 epoxide equivalents of the alkylene oxide and 0.5 to 1.9 epoxide equivalents of the cyclohexane epoxide.

20. Organo silicon compounds prepared by reaction of l) a halosilane of the formula SiX; wherein X is halogen with (2) a monohydric alcohol or a combination of a monohydric alcohol and an alkylene oxide with (3) an epoxide selected from the group consisting of an epxoide having the formula CH -CHCH OR-,

wherein R is selected from the group consisting of phenyl and the amino, halogen and alkyl substituted derivatives thereof, alkyl, alkenyl, acrylo and methacrylo; an epoxide of the formula CH CHCH R;,-CH -CHCH O 0 wherein R is a divalent organic group selected from the group consisting of alkylene, alkyleneoxyalkylene, oxyalkyleneoxy, oxyalkyleneoxyalkyleneoxy, a group having the formula and a group having the formula and a cyclohexane epoxide, writh the ratio of the num ber of epoxide equivalents of (3) to the number of alcohol is selected from the group consisting of an alkanol, benzyl alcohol, allylalcohol and alkanol amines.

23. A compound having the formula n wherein X is halogen, R is hydrogen or alkyl, R is selected wherein X is halogen, R is hydrogen or alkyl, R is selected from the group consisting of phenyl and the amino, halogen and alkyl substituted derivatives thereof, alkyl, alkenyl, acrylo and methacrylo, x is an integer from 2m 3 and y is an integer from 1 to 2.

24. A compound as defined in claim 23 whefein R is alkenyl.

25. A compound as defined in claim 23 wherein R is acrylo or methacrylo.

26.A compound as defined in claim 23 wherein the compound has the formula Cl Cl 27. A compound as defined in claim 23 wherein the compound has the formula 28. A compound as defined in claim 23 wherein the compound has the formula 29. A compound having the formula wherein R is hydrogen or alkyl and X is halogen.

30. A compound having the formula R, -cii cH )=,Si-ocii. cH cH -o R,-o- I I and a group of the formula,

2. R is hydrogen or alkyl and X is halogen.

31. A compound as defined in claim 30 wherein the compound has the formula 32. A compound as defined in claim 30 wherein the compound has the formula 33. A compound selected from the group consisting of a compound having the formula (R[,-O ),Si( O\Cl-l(Il-lR O-CH2CHCH2-OR) wherein R is a divalent organic group selected from the group consisting of alkylene, alkyleneoxyalkylene,

oxyalkyleneoxy, oxyalkyleneoxyalkyleneoxy, a group having the formula and a group having the formula 34. A compound as defined in claim 33 wherein R is hdrygoen.

35. Organo silicon group compounds prepared by reaction of 1) an organo silane having the formula wherein R is selected from the group consisting of alkyl, alkenyl, cycloalkyl and phenyl, X is halogen and n is an integer from 1 to 2, with (2) a compound selected from the group consisting of an alkylene oxide, a monohydric alcohol and a combination thereof and (3) an epoxide selected from the group conisting of an epoxide of the formula CH- CHCH --R wherein R is selected from the group consisting of phenyl and the amino, halogen and alkyl substituted derivatives thereof, alkyl, alkenyl, acrylo and methacrylo; an epoxide of the formula wherein R is a divalent organic group selected from the group consisting of alkylene, alkyleneoxyalkylene, oxyalkyleneoxy, oxyalkyleneoxyalkyleneoxy, a group having the formula and a group having the formula and a cyclohexane epoxide, with the ratio of the number of epoxide equivalents of (3) to the number of moles of (1) being less than 2 when the epoxide (3) contains two or more epoxy groups per mole.

36. Compounds as defined in claim 35 wherein n is l.

37. Compounds as defined in claim 35 wherein the reaction is carried'out with 1 to 2 moles of said compound and 0.5 to 3 moles of the epoxide per mole of the silane.

' 38. Compounds as defined in claim 35 wherein said compound is an alkylene oxide.

39. Compounds as defined in claim 35 wherein said compound is a monohydric alcohol.

40. Organo silicon compounds prepared by reaction of 1) an organo silane having the formula (R7)1| (4-ll) wherein R is selected from the group consisting of alkyl, alkenyl, cycloalkyl, phenyl, X is halogen and n is an integer from 1 to 2, with an epoxide selected from the group consisting of an epoxide of the formula wherein R is selected from the group consisting of phenyl and the amino, halogen and alkyl substituted derivatives thereof, alkyl, alkenyl, acrylo and methacrylo.

41. A compound selected from the group consisting of a compound of the formula wherein R, is selected from the group consisting of al- 'kyi, alkenyl, cycloalkyl, phenyl, X is halogen, R is selected from the group consisting of phenyl and the amino, halogen and alkyl substituted derivatives thereoflalkyl, alkenyl, acrylo and methacrylo, e is an integer from l to 2 and f is an integer from the l to 2; and a compound of the formula wherein R is a divalent organic group selected from the group consisting of alkylene, alkyleneoxyalkylene, oxyalkyleneoxy, oxyalkyleneoxyalkyleneoxy, a group having the formula and a group having the formula 42. A compound as defined in claim4l wherein f is l.

43. A compound selected from the group consisting of a compound of the formula wherein vR is a divalent organic group selected from the group consisting of alkylene, alkyleneoxyalkylene, oxyalkyleneoxy, oxyalkyleneoxyalkyleneoxy, a group having the formula and a group having the formula 44. A compound having the formula wherein R is hydrogen or methyl.

47. A compound as defined in claim 44 wherein the compound has the formula 48. A compound as defined in claim 44 wherein the compound has the formula 49. Organo silicon compounds prepared by reaction of silicon tetrachloride with an alkylene oxide and a compound selected from the group consisting of the compound of the formula and "o-cn -cK-cn with the ratio of the number of epoxide equivalents of said compounds to the number of moles of silicon tetrachloride being less than 2. 

1. ORGANO SILICON COMPOUNDS PREPARED BY REACTION OF (1) A HALOSILANE SELECTED FROM THE GROUP CONSISTING OF A SILANE OF THE FORMULA SIX4 WHEREIN X IS HALOGEN, AND A COMPOUND OF THE FORMULA (R7)MSIX(4-N) WHEREIN R7 IS AN ORGANIC GROUP SELECTED FROM THE GROUP CONSISTING OF ALKYL ALKENYL, CYCLOALKYL AND PHENYL, X IS HALOGEN AND N IS AN INTEGER FROM 1 TO 2, WITH (2) A COMPOUND SELECTED FROM THE GROUP CONSISTING OF A MONOHYDRIC ALCOHOL, AN ALKYLENE OXIDE AND A COMBINATION THEREOF AND (3) AN EPOXIDE SELECTED FROM THE GROUP CONSISTING OF AN EPOXIDE OF THE FORMULA
 2. Compounds as defined in claim 1 wherein the halosilane is SiX4 and the reaction is carried out with 1 to 3 epoxide or hydroxy equivalents of said compound and 1 to 3 epoxide equivalents of (3) per mole of the halosilane.
 3. Compounds as defined in claim 1 wherein X is selected from the group consisting of chlorine and bromine.
 4. Compounds as defined in claim 1 wherein the halosilane is SiX4.
 5. Compounds as defined in claim 4 wherein said compound is an alkylene oxide.
 6. Compounds as defined in claim 4 wherein said compound is a monohydric alcohol.
 7. Compounds as defined in claim 4 wherein said compound is a mixture of an alkylene oxide and a monohydric alcohol.
 8. Compounds as defined in claim 1 wherein the halosilane is (R7)nSiX(4-n).
 9. Compounds as defined in claim 1 wherein the halosilane is R7SiX3.
 10. Compounds as defined in claim 9 wherein the reaction is carried out with 1 to 2 epoxide or hydroxy equivalents of said compound and 1 to 2 epoxide equivalents of (3) per mole of the halosilane.
 11. Organo silicon compounds prepared by reaction of a halosilane of the formula SiX4 wherein X is halogen with an alkylene oxide and an epoxide having the formula
 12. Compounds as defined in claim 11 wherein the reaction is carried out with 1 to 3 epoxide equivalents of the alkylene oxide and 1 to 3 epoxide equivalents of said epoxide.
 13. Compounds as defined in claim 11 wherein the product includes compounds of the formula
 14. Organo silicon compounds prepared by reaction of a halosilane of the formula SiX4 with an alkylene oxide and an epoxide having the formula
 15. Compounds as defined in claim 14 wherein the product contains compounds of the formula
 16. Compounds as defined in claim 14 wherein the product includes compounds of the formula
 17. Compounds as defined in claim 14 wherein the reaction is carried out by reacting the alkylene oxide with the halosilane and then reacting the resulting product with said epoxide.
 18. Organo silicon compounds prepared by reaction of a halosilane of the formula SiX4 wherein X is halogen with an akylene oxide and a cyclohexane epoxide selected from the group consisting of
 19. Compounds as defined in claim 18 wherein the reaction is carried out with 2.1 to 3.0 epoxide equivalents of the alkylene oxide and 0.5 to 1.9 epoxide equivalents of the cyclohexane epoxide.
 20. Organo silicon compounds prepared by reaction of (1) a halosilane of the formula SiX4 wherein X is halogen with (2) a monohydric alcohol or a combination of a monohydric alcohol and an alkylene oxide with (3) an epoxide selected from the group consisting of an epxoide having the formula
 21. Compounds as defined in claim 20 wherein the reaction is carried out with 1 to 3 moles of the alcohol, 0 to 2 moles of the alkylene oxide and 0.5 to 3 epoxide equivalents of the epoxide per mole of halosilane.
 22. Compounds as defined in claim 20 wherein the alcohol is selected from the group consisting of an alkanol, benzyl alcohol, allylalcohol and alkanol amines.
 23. A compound having the formula n
 24. A compound as defined in claim 23 whefein R2 is alkenyl.
 25. A compound as defined in claim 23 wherein R2 is acrylo or methacrylo.
 26. A compound as defined in claim 23 wherein the compound has the formula
 27. A compound as defined in claim 23 wherein the compound has the formula
 28. A compound as defined in claim 23 wherein the compound has the formula
 29. A compound having the formula
 30. A compound having the formula
 31. A compound as defined in claim 30 wherein the compound has the formula
 32. A compound as defined in claim 30 wherein the compound has the formula
 33. A compound selected from the group consisting of a compound having the formula
 34. A compound as defined in claim 33 wherein R5 is hdrygoen.
 35. Organo silicon group compounds prepared by reaction of (1) an organo silane having the formula (R7)nSiX(4-n) wherein R7 is selected from the group consisting of alkyl, alkenyl, cycloalkyl and phenyl, X is halogen and n is an integer from 1 to 2, with (2) a compound selected from the group consisting Of an alkylene oxide, a monohydric alcohol and a combination thereof and (3) an epoxide selected from the group conisting of an epoxide of the formula
 36. Compounds as defined in claim 35 wherein n is
 1. 37. Compounds as defined in claim 35 wherein the reaction is carried out with 1 to 2 moles of said compound and 0.5 to 3 moles of the epoxide per mole of the silane.
 38. Compounds as defined in claim 35 wherein said compound is an alkylene oxide.
 39. Compounds as defined in claim 35 wherein said compound is a monohydric alcohol.
 40. Organo silicon compounds prepared by reaction of (1) an organo silane having the formula (R7)n SiX(4-n) wherein R7 is selected from the group consisting of alkyl, alkenyl, cycloalkyl, phenyl, X is halogen and n is an integer from 1 to 2, with an epoxide selected from the group consisting of an epoxide of the formula
 41. A compound selected from the group consisting of a compound of the formula
 42. A compound as defined in claim 41 wherein f is
 1. 43. A compound selected from the group consisting of a compound of the formula
 44. A compound having the formula
 45. A compound as defined in claim 44 wherein R2 is alkenyl.
 46. A compound as defined in claim 44 wherein R2 is a group
 47. A compound as defined in claim 44 wherein the compound has the formula
 48. A compound as defined in claim 44 wherein the compound has the formula
 49. Organo silicon compounds prepared by reaction of silicon tetrachloride with an alkylene oxide and a compound selected from the group consisting of the compound of the formula 